Chloroethylation of alkylated benzene compounds



Patented Aug. 1, 1950 CHLOROETHYLATION OF ALKYLATED BENZENE COMPOUNDS Eugen Gottfried Galitzenstein, London, Francis Edward Salt, Banstead, Herbert Muggleton Stanley, Tadworth, and Thomas Weir, Epsom, England, assignors to The Distillers Company, Limited, Edinburgh, Scotland, a British com- No Drawing. Application October 17, 1946, Serial No. 703,706. InGreat Britain October 22,

invention relates to an improved. process for the manufacture of alpha-chloroethyl alkyl benzenes, by the chloroethylation of polymethylsubstituted benzenes'such as m-xylene, pseudo cumene and mesitylene.

It is known that alpha-chloroethyl-xylene can be prepared by reacting m-xylene with paraldehyde and aqueous hydrochloric acid in the presence of a. low boiling diluent or solvent such as petroleum ether, but in the absence of any metal salts acting as condensing agents. The yields of alpha-chloroethyl Xylene obtained by this process, however, are very unsatisfactory.

' According to the present invention there is provided a process for the manufacture of chloroethyl-alkyl .benzenes which comprises condensing di(alpha-chloroethyl) ether with a polymethyl-substituted benzene in the presence of zinc chloride at a temperature between 15 C. and +15 C. the reaction mixture being adjusted to contain not more than 50% by weight of water calculated upon the weight of zinc chloride used. The reaction is facilitated by the presence of hydrogen chloride which maybe dissolved in the polymethyl benzene or passed into the reaction mixture.

The di(alpha-ch1oroethyl) ether may be prepared in situ by the interaction of hydrogen chloride with acetaldehyde or substances decomposable, under the reaction conditions, to yield acetaldehyde, for example, by passing a current of gaseous hydrogen chloride into a liquid mixture comprising the polymethyl-substituted benzene and acetaldehyde, in the presence of zinc chloride, as condensing agent, whilst maintaining the reaction mixture at a temperature between 15 C. and +15=C. and limiting the water content thereof as above stated. In this reaction, apparently, the formation of di(alpha-chloroethyl) ether first takes place according to the equation .'2CI-I3LCHO+2HCl=(CI-I3CHC1) 2O+H2O and the ether thus formed then condenses under the influence of the zinc chloride, with the polymethyl-benzene.

The optimum reaction temperature may vary slightly with the methylated benzene to be chloroethylated. Thus, for instance, the chlorcethylation of m-xylen'e is best carried out at C., whilst a temperatureof C. is found to be most advantageous for the chloroethylation of mesitylene, The reaction with pxylene results in very small yields only. g g

Instead of acetaldehyde, substances such as paraldehyde, which decompose to yield acetal- 7 Claims. (01. 260651) dehyde under the reaction conditions may beused.

We have observed that the presence of water will decrease the rate of substitution and will even inhibit the reaction when the quantity exceeds by weight of the zinc chloride used. As water is formed during the reaction, we have found it advantageous to restrict the amount of water initially present by excluding water from the reaction mixture at the start and adding the zinc chloride" in' the anhydrous state-preferably in finely divided form, or as an aqueous solution which does not contain more than 25% feet: Example I.212 g. of pure m-xylene were mixed with 30 gfiof powdered anhydrous zinc chloride, cooled to about 0 C. and saturated with dry hydrogen chloride with vigorous agitation. 44 g. of paraldehyde were slowly added to the cooled agitated reaction mixture over a Stirring was continuedfor a further 3 /2 hours, the temperature being maintained at about 0 C. A slow stream of period of half an hour.

while the upper layer was washed with ice-water until it was free from hydrochloric acid and zinc salt. It was then' dried and fractionally distilled in vacuo.

retical based on the paraldehyde used.

Instead of using pure m-xylene as raw material, a commercial mixture which is substan tially free from unsaturated compounds, such as is known under the trade name Chemists Xylene and containingabout by weight of m-xylene, may be used.

Example II.-A mixture of g. of isomeric trimethylbenzenes (containing mesitylene and pseudo-,cumene) with 3Q g. of powdered anhydrous zinc chloride was reacted with 44 g; of paraldehyde in the mannerdeseribed in Example I, but maintaining thetemperature of the mixture at about 10 C. j The yield of alphachloroethyl trimethylbenzenes 715% of the theoreticalbased on the paralde hyde employed. 7 l

An alternative way to; thatdescribed above oi carrying the invention'into effect consists in first y. weight of water." The hydrogen chloride used is preferably free from moisture.

The following example illustrates the manner-- in which the invention may be carried into ef-,

The yield ofdistilled alpha-chloro-- ethyl m-xylene amounted to 71.3% of the theoamounted tov preparing the di(alphachloroethyl) ether, separating it from.the.. watercf ormed.in that reaction and thenproceedi'ng withithe condensation reaction in the presence of zinc chloride. To carry out this process acetaldehyde, or substances de-... composable, under the reaction conditions, to yield acetaldehyde, is dissolved'dni'th'eipolymetm yl-substituted benzene and then hydrogen chlor-n ride is passed through the reactionrmixturewhich.

is maintained at the stated.:.low., temperature; 101,

When the reaction mixture is'zsaturated with.hyr drogen chloride and the acetaldehydeehas.+been.,.: converted into the chlorine-substitfltdrthersthe:2- water formed separates in the form of an aqueous layer which is removed, for instance by. decantae tion. By bringing the remaining.,mixture-, keeping it at the stated low temperatures, in contact with zinc chloride, the condensation between the chlorinated ether and the polymethyl sub' stituted benzene is effected and the following examplesillustrate thi's alternative :method:

Example III.-A mixture of 39.6 g. of paraldea hyae in 170' cczaofr commercial: xylene free from unsaturated compounds1*.(Chemists Xylene) was saturated with dry 'hydrogen' chloride at: about 0. cilfiivhilst istirringx: The-*mixturerformed' two layerstthe lowertaqueous slayer-"was." separated and the =upper slayer containing the" di (alpha-chloroethyl) ether wasfsl'owly 'addetlrover aperiod of '55 minutes to -a cooled agitated'mixture of: 20 g. of 3 purezinc chloride suspended; M12200. cc: :of -xylene which h'adi previously been saturatedwithhydro gen chloride; After'ra .zf'urther period .of three. hours, '51. during whichthe reaction" mixture was stirred and maintained" at .iabout- 20? C." the reac-'- a. tidn product wasworkedviip'xasdescribed in :EX- ampIe I-Jfi The-yield of idistilledialphaechloroethyl xylene amounted to 69% of the theoretical based; on time 'paraldehydesusedc EZI JGmpZE F'IVFTAiSOIHfiGII of' the difalpha-chlo r'oethirllether. in xyleneciwassprepared asde scribed in'fli'xample 270: g.-"=of this solutionwere slowly'saddedduring a period' of .45 minutes to 106 grof xyleneatcfwhich 3155 g. ofamixture' ofi'izinc v chloridetandaiwaterg ini the proportion of 80 'parts by weight ofrsthez-former 1-to; 20.--parts byweight f water; haverbeen added. The imixture. was agitated 'io'r'ra furtherwfl%,:ihours;--the temv peraturetrthronghout being". maintained at about 0%01 i. Theiresultingreactiomproductwas worked upaaswdescribed 'JiHfEXEi-IIIIJTG IL The yieldof dis?- tilled? -'alpha:-"chloroethyl z xylene "was 64 of the theoretical based onstheparaldehyde used.

' Bgt 'carryingi-.out:wrthe*sohloroethylation: process according to thi's invention, the; formation of= res-;

inous: matter as wellz-iasot-diaryl :ethanecom pounds in any considerable quantitycis avoided andsgoo'd yieldsaof-xthe'chloroethylated arylcompounds: are :obtained. w

I The :chloroethyl-substituted-- polymethyl ben-' zenes-rmaybe rconverted; byelimination of 'hydro- 6O sent-chloride, .in' any well-known manner, into valuable nuclear methyl-substituted styrene come pounds;

A. process-for the separation..of...ethylbenzene from, sorvits concentration in,..hydrocar.bon -mix.-.. tu'res containing isomeriaxylenes. employing. the herein. :described ..chloroethy1ation process. is .de-. scribed Min copendingi British application.- .No'. 27108745. 'of even date herewith.

The expression compound yielding .acetaldehyde as employed in the appended claims is .in-.. tended "to designate acetald'ehyde, paraldehyde. and compounds decomposable under the-reaction conditions .to' yield acetaldehyde.

4 What we claim is: 1.1.A.process-.for the manufacture .of chloroethyl alkylibenzenes which comprises condensing di(alpha-chloroethyl) ether with a polymethyl- 5 sub'stituted benzene in the presence of zinc chloride at a temperature between -l5 C. and +15 Cilthezreactionmixture being adjusted to contain not more than 50% by weight of water calculated uponthe weight of zinc chloride used.

2.1JA"pr.o.cess.. according to claim 1 wherein a stream .of 'hydrogen: chloride is passed into the reactionmixtureii.

3....Aiiprocess --for; the manufacture of chloroethyl-alkyl benzenestwhich comprises condensing idiialpha-chloroethyl) ether with a Xylene in the presence ofi zinc .chloride at a temperature between 15 C. and'\+15 C. the reaction mixture being adjusted to contain not more than 50% by weigh'fl'of water calculated upon the weight of zinc chloride used.

ethylealkyl:benzeneswhichcomprisescondensing? diialphawhloroet-hyl) ether with mxylene inthe presence -'0f':IZiIlC. chloride at. a temperature of. about 0 C. the reaction mixture. being adjustedtoacontainnotmore than 50% byweightof water calculated uponrthe weight of. .zinc chloride used;

5..- A process for. :-the manufacture of. chloroethyl-alkyl,benzeneswhich. comprises condensingdiialpha chloroethyli ether with. mesitylene. inv the presence-of zinc .chlorideata temperature oi.

about. 1 0.9-. C. the reaction miXtureJbeingadjustP ed to contain not. more.than..50.%..by weight of water calculated upon the weight of zinc. chloride used...

GCA process according to claim 4 in'whichi the difalpha-chloroethyl) .ethenisproduced by. pass-1 ing', "a current of "gaseous hydrogen chloride through a'liquidmixture'of' in xylene and a com pound-yieldingacetaldehyde, and then bringing the reaction mixture into contact with zinc'ch1o'' rideto effect condensation of thedi (alpha-chloroethyl') ether and m-Xylene.

'7. "A processin accordance with 'claim 4 in which the 'di (-a1pha-chloroethyl) 'ether is" pro-' duced-"by passinga current of gaseous hydrogen-v chloride through a liquid mixture of m-xylene= and a 1 compoundyielding acetaldehyde; separatingsthe' aqueous layer: formed upon conversion of their acetaldehyde into di (alphachloroethyl) ether, and bringing the resulting reaction mixture containing said'ethersinto contact with zinc chlo-' ridetoefiecttheicon'densation of-said ether and said Lin-xylene;

EUGEN:IGOT'IFRIED GALITZENSTEIN... FRANCIS EDWARD. SALT..

HERBERT lM'UGGLETONJ STANLEY.

THOMAS W EIR: p

REFERENCES. CITED The following references are of record-inzth file; of; this i-patent:

STATES PATENTS Number Name Date 1,9261314. Smith Sept. 12,1933 2,219,873 Pinkernelle ..Oct.29,'1940 OTHER REFERENCES Adams 'et 'a1.: Organic Reactions, vol; 1, pages 66-73 (194-2).

Stephens eta1.:' Jour. Chem. Soc. (London); 1920, pages 515-519. 

1. A PROCESS FOR THE MANUFACTURE OF CHLOROETHYL-ALKYL BENZENES WHICH COMPRISES CONDENSING DI(ALPHA-CHLOROETHYL) ETHER WITH A POLYMETHYLSUBSTITUTED BENZENE IN THE PRESENCE OF ZINC CHLORIDE AT A TEMPERATURE BETWEEN -15*C. AND +15* C. THE REACTION MIXTURE BEING ADJUSTED TO CONTAIN NOT MORE THAN 50% BY WEIGHT OF WATER CALCULATED UPON THE WEIGHT OF ZINC CHLORIDE USED. 